US4471144A - Theta-alumina as a hydrothermally stable support in hydrogenation - Google Patents
Theta-alumina as a hydrothermally stable support in hydrogenation Download PDFInfo
- Publication number
- US4471144A US4471144A US06/449,044 US44904482A US4471144A US 4471144 A US4471144 A US 4471144A US 44904482 A US44904482 A US 44904482A US 4471144 A US4471144 A US 4471144A
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- United States
- Prior art keywords
- alumina
- theta
- hydrogenation
- catalyst
- temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
Definitions
- the irony in hydrogenating aqueous solutions of carbohydrates is two-fold.
- One aspect of this invention is a method of hydrogenating hydrogenatable organic material in aqueous solution using as a catalyst a metal on theta-alumina as a hydrothermally stable support.
- this invention is a method of hydrogenating an aqueous solution of a carbohydrate where the catalyst is a Group VIII zerovalent metal dispersed on a support of theta-alumina.
- the metal is ruthenium.
- the carbohydrate is a hexose.
- One aspect of this invention is a method of hydrogenating a hydrogenatable organic material in aqueous solution comprising contacting the aqueous solution with hydrogen under hydrogenation conditions in the presence of a metal which is a hydrogenation catalyst dispersed on theta-alumina, and recovering the hydrogenated product.
- Another aspect of the invention which is the subject matter herein is a method for the hydrogenation of a carbohydrate in aqueous solution to its polyols comprising contacting at hydrogenation conditions a reaction medium consisting essentially of said solution with hydrogen and a catalyst consisting essentially of ruthenium dispersed on theta-alumina, and recovering the formed polyols.
- This invention results from the discovery that theta-alumina possesses remarkable hydrothermal stability under conditions necessary for the hydrogenation of aqueous solutions of hydrogenatable organic materials, particularly carbohydrates, especially in comparison with the more commonly used gamma-alumina.
- substantial amounts of silica and gamma-alumina which are two commonly employed support materials, dissolve in the aqueous medium during hydrogenation of, for example, carbohydrates, virtually no leaching of theta-alumina occurs under comparable hydrogenation conditions.
- one advantage of this invention is that the product contains a substantially lower level of dissolved metal from the inert support described herein than that resulting from inert supports commonly employed previously in the hydrogenation of aqueous solutions of carbohydrates.
- Another advantage of this invention is that the metals commonly employed as a hydrogenation catalyst retain their activity on the theta-alumina support of this invention.
- Yet another advantage of the invention as claimed is that of the Group VIII metals ruthenium is more resistant to leaching under hydrogenation conditions than other Group VIII metals. Because ruthenium is both resistant to leaching and particularly catalytically active it is especially advantageous in the practice of this invention.
- one aspect of the invention herein is a method of general utility for the hydrogenation of a hydrogenatable organic material in aqueous solution.
- the crux of this aspect of the invention is the use as a hydrogenation catalyst of a metal dispersed on theta-alumina.
- the metals used are those known to be effective in catalyzing hydrogenation.
- the essence of this aspect of the invention is the use of theta-alumina as a hydrothermally stable support for metals catalytically active in hydrogenation, thereby conferring advantages on a method utilizing such a metal-support combination for hydrogenation in an aqueous medium.
- metals which may be used are vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, technetium, ruthenium, rhodium, palladium, silver, tungsten, rhenium, osmium, iridium, and platinum.
- metals will be in their zerovalent state, but some metallic compounds, such as copper chromite, are catalytically active per se, not being reduced to their zerovalent state even in situ.
- the hydrogenation conditions include such variables as temperature, hydrogen pressure, and catalyst concentration, which will depend on the particular metal used and specific organic material to be hydrogenated, inter alia.
- a catalyst concentration from about 0.001 to about 0.5% metal
- a temperature from about 50° C. to about 200° C.
- a hydrogen pressure from one atmosphere up to several atmospheres will suffice.
- an aromatic compound as a substrate, for example benzene, and the same metal and concentration as before, a somewhat higher temperature from about 125° C. to about 250° C. at a pressure from several to several hundred atmospheres are appropriate.
- it is not feasible to list all appropriate hydrogenation conditions these are readily determined by one skilled in the art in the practice of this invention.
- Carbohydrates are polyhydroxyaldehydes, polyhydroxyketones, or compounds that can be hydrolyzed to them.
- a carbohydrate that cannot be hydrolyzed to simpler compounds is called a monosaccharide.
- One that can be hydrolyzed to two monosaccharide molecules is called a disaccharide, and one that can be hydrolyzed to many monosaccharide molecules is called a polysaccharide.
- a monosaccharide may be classified according to the number of carbon atoms it contains; a hexose is a 6-carbon monosaccharide, a pentose is a 5-carbon monosaccharide, and a tetrose is a 4-carbon monosaccharide.
- Monosaccharides are preferred among the carbohydrates which may be used in this invention, and among these the hexoses, pentoses and tetroses are the most important members, with the hexoses particularly preferred.
- the polyol reduction products of this invention have the formula HOCH 2 (CHOH) n CH 2 OH, where n is 2, 3, or 4 depending upon the kind of monosaccharide used or the kind of units in the di- or polysaccharide.
- n 4, the polyol is a hexitol; where n is 3, the polyol is a pentitol; and where n is 2, the polyol is a tetritol. It is to be understood that where the carbohydrate is a disaccharide or polysaccharide, substantial hydrolysis accompanies hydrogenation to ultimately afford the polyols of this invention.
- monosaccharides that can be employed include glucose, mannose, galactose, talose, fructose, allose, altrose, idose, gulose, xylose, lyxose, ribose, arabinose, threose and erythrose.
- Glucose and mannose are particularly preferred monosaccharides which afford sorbitol and mannitol, respectively, as their polyol reduction product.
- Fructose is another preferred monosaccharide which affords a mixture of sorbitol and mannitol as the product.
- disaccharides include maltose, cellobiose, sucrose and lactose.
- starch, cellulose and their degradation products are starch, cellulose and their degradation products.
- the catalyst of this aspect of the invention consists essentially of zerovalent ruthenium dispersed on theta-alumina.
- a catalyst is prepared by impregnating theta-alumina with a suitable ruthenium salt, optionally calcining the salt, and reducing it to the zerovalent metal in a hydrogen atmosphere. It has been found that although calcination in an inert atmosphere at a temperature from about 200° C. to about 500° C. affords a satisfactory catalyst, it is preferable to omit the calcination and reduce the ruthenium salt in flowing hydrogen at a temperature between about 140° C. and about 500° C., but preferably between about 300° C. and about 500° C.
- theta-alumina is meant alumina whose crystallinity as measured by X-ray diffraction corresponds to that characterized in the Joint Committee on Powder Diffraction Standards number 23-1009. Because the surface area of theta-alumina is low relative to, e.g., gamma-alumina, metal loadings are correspondingly low. In this invention the catalyst typically contains from about 1 to about 10% metal.
- the aqueous solution of the carbohydrate is contacted with hydrogen and the catalyst of this invention at hydrogenation conditions.
- Hydrogenation conditions include a pressure of at least about 200 psig, with pressures in excess of about 5000 psig generally not advantageous. In the usual case, a hydrogen pressure from about 700 to about 5000 psig is used, with a pressure from about 1000 to about 3000 psig preferred.
- the hydrogenation temperature will be greater than about 80° C., with the upper temperature limit dictated by the onset of the decomposition of either the product or reactant. For example, in the case of glucose as the reactant and sorbitol as the product, the upper temperature limit is about 160° C. In practical terms, a hydrogenation temperature from about 100° to about 150° C. is preferred with one from about 105° to about 130° C. being especially advantageous.
- the amount of catalyst used will depend, inter alia, on the amount of metal on the support, hydrogenation pressure, and temperature. Usually, sufficient catalyst is employed to give from about 0.1 to about 1 wt. % ruthenium based on the carbohydrate as monosaccharide.
- the method of this invention may be practiced in either a batch or a fixed mode.
- a batch mode an aqueous solution of the carbohydrate containing from about 25 to about 60 percent carbohydrates is loaded into a reactor containing the ruthenium on theta-alumina catalyst of this invention in an amount sufficient to give from about 0.1 to about 1 wt. % ruthenium based on the carbohydrate.
- the mixture is then heated to the desired temperature, which is from about 80° to about 160° C., and usually from about 1OO° to about 150° C.
- hydrogen is admitted to a pressure from about 700 to about 5000 psig.
- the entire reaction mixture is then agitated to provide adequate contact among the hydrogen, catalyst, and carbohydrate.
- the hydrogenation is continued until there is no further hydrogen uptake, which generally is a time from about 0.5 to about 5 hours.
- the invention described is advantageously practiced in a continuous fashion using the catalyst in a fixed bed, fluidized bed, expanded bed, and so forth.
- feedstock containing from about 25 to about 60% of the carbohydrate(s) to be reduced is passed through the bed of ruthenium on theta-alumina in a hydrogen atmosphere.
- Hydrogen pressure is from about 700 to about 5000 psig, and bed temperature is generally from about 100 to about 150° C.
- the effluent is an aqueous solution of the formed polyol(s), which may be recovered, for example, by removal of water by evaporation.
- Catalyst A was calcined in nitrogen at 410° C., then reduced at 410° C.
- Catalyst B was not calcined and was reduced at 410° C.
- Catalyst C also was not calcined but was reduced at 145° C. Continuous reductions were performed over a fixed bed of each catalyst at 2300 psig hydrogen at 1.0 LHSV for at least 200 hours, with the range of observed results presented in Table 3.
- Comparison of entries for A and B shows that omitting calcination affords a more active catalyst, as indicated by the lower operating temperature.
- the conversion with catalyst A declined over a 200 hour test run whereas that with catalyst B remained steady, showing that the absence of calcination affords a more stable catalyst, i.e., one with a longer effective lifetime.
- Catalyst C shows that lowering the reduction temperature adversely affects the selectivity characteristics of the resulting catalyst.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
TABLE 1 ______________________________________ Continuous Reduction of Glucose, 3% Ru on Theta-Alumina, Calcined in N.sub.2 @ 410°C., Reduced in H.sub.2 @ 410° C. p.sup.a T.sup.b LHSV.sup.c Conversion.sup.d Selectivity.sup.e ______________________________________ 700 120 1.0 97 96 700 120 0.5 98 94 700 120 2.0 63 96 2000 120 2.5 76 97 2000 120 1.0 99 97 2000 120 0.5 99 96 1500 120 1.0 99 2000 120 1.5 93 97 700 120 1.0 86 96 700 130 1.0 94 94 700 110 1.0 72 97 ______________________________________ .sup.a Hydrogen pressure, psig .sup.b Temperature, °C. .sup.c Liquid hourly space velocity .sup.d Percent glucose reacted .sup.e Percentage of sorbitol in total product mix. Other products includ mannitol, fructose, and iditol.
TABLE 2 ______________________________________ Leaching in Continuous Reduction Time on Stream (hrs) Al, ppm Ru, ppm ______________________________________ 12 9.4 <1 32 4.8 84 0.4 <1 180 0.2 <1 252 0.3 <1 ______________________________________
TABLE 3 ______________________________________ Effect of Catalyst Preparation of Continuous Reduction of Glucose Catalyst T, °C. Conversion Selectivity ______________________________________ A 120 99.4-99.9 92.2-94.0 B 106 99.8-99.9 91.6-94.0 C 110 99.8-99.9 85.7-88.4 ______________________________________
Claims (10)
Priority Applications (1)
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US06/449,044 US4471144A (en) | 1982-12-13 | 1982-12-13 | Theta-alumina as a hydrothermally stable support in hydrogenation |
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US06/449,044 US4471144A (en) | 1982-12-13 | 1982-12-13 | Theta-alumina as a hydrothermally stable support in hydrogenation |
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US4471144A true US4471144A (en) | 1984-09-11 |
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US06/449,044 Expired - Fee Related US4471144A (en) | 1982-12-13 | 1982-12-13 | Theta-alumina as a hydrothermally stable support in hydrogenation |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0949233A2 (en) * | 1998-04-07 | 1999-10-13 | Basf Aktiengesellschaft | Process for the preparation of sugar alcohols |
US20040002597A1 (en) * | 1999-03-16 | 2004-01-01 | Sudzucker Aktiengesellschaft | Catalytic process for the modification of carbohydrates, alcohols, aldehydes or polyhydroxy compounds |
US6693060B2 (en) * | 2001-05-18 | 2004-02-17 | Korea Research Institute Of Chemical Technology | Modified θ-Al2O3-supported nickel reforming catalyst and its use for producing synthesis gas from natural gas |
US20040171889A1 (en) * | 2001-06-11 | 2004-09-02 | Dominic Vanoppen | Method for the production of sorbit |
US20040176619A1 (en) * | 2001-06-11 | 2004-09-09 | Dominic Vanoppen | Ruthenium catalysts on a s102-based carrier material for catalytic hydrogenation of saccharides |
US20050054738A1 (en) * | 2003-09-08 | 2005-03-10 | Conocophillips Company | Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts |
US20060009661A1 (en) * | 2002-12-11 | 2006-01-12 | Basf Aktiengesellschaft | Continuous method for the production of sugar alcohols |
WO2006061196A1 (en) * | 2004-12-07 | 2006-06-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Method for the production of sugar alcohols |
US20080139383A1 (en) * | 2006-03-27 | 2008-06-12 | Catalytic Distillation Technologies | Hydrogenation of aromatic compounds |
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US2868847A (en) * | 1956-10-05 | 1959-01-13 | Engelhard Ind Inc | Hydrogenation of mono-and disaccharides to polyols |
US4221738A (en) * | 1979-03-05 | 1980-09-09 | Uop Inc. | Production of acrylonitrile |
US4235705A (en) * | 1978-12-15 | 1980-11-25 | Uop Inc. | Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite |
US4264475A (en) * | 1978-08-16 | 1981-04-28 | Mobil Oil Corporation | Bimetallic reforming catalyst containing separate platinum-containing and iridium-containing particles |
US4303552A (en) * | 1980-05-27 | 1981-12-01 | W. R. Grace & Co. | Diesel exhaust catalyst |
US4323542A (en) * | 1979-06-27 | 1982-04-06 | Uop Inc. | Catalytic conversion of carbon monoxide, hydrocarbons and oxides of nitrogen |
US4338221A (en) * | 1981-02-11 | 1982-07-06 | Uop Inc. | Catalyst for the reduction of unsaturated organic acids |
US4380680A (en) * | 1982-05-21 | 1983-04-19 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
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1982
- 1982-12-13 US US06/449,044 patent/US4471144A/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US2868847A (en) * | 1956-10-05 | 1959-01-13 | Engelhard Ind Inc | Hydrogenation of mono-and disaccharides to polyols |
US4264475A (en) * | 1978-08-16 | 1981-04-28 | Mobil Oil Corporation | Bimetallic reforming catalyst containing separate platinum-containing and iridium-containing particles |
US4235705A (en) * | 1978-12-15 | 1980-11-25 | Uop Inc. | Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite |
US4221738A (en) * | 1979-03-05 | 1980-09-09 | Uop Inc. | Production of acrylonitrile |
US4323542A (en) * | 1979-06-27 | 1982-04-06 | Uop Inc. | Catalytic conversion of carbon monoxide, hydrocarbons and oxides of nitrogen |
US4303552A (en) * | 1980-05-27 | 1981-12-01 | W. R. Grace & Co. | Diesel exhaust catalyst |
US4338221A (en) * | 1981-02-11 | 1982-07-06 | Uop Inc. | Catalyst for the reduction of unsaturated organic acids |
US4380680A (en) * | 1982-05-21 | 1983-04-19 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0949233A3 (en) * | 1998-04-07 | 2000-01-12 | Basf Aktiengesellschaft | Process for the preparation of sugar alcohols |
US6177598B1 (en) | 1998-04-07 | 2001-01-23 | Basf Aktiengesellschaft | Preparation of sugar alcohols |
EP0949233A2 (en) * | 1998-04-07 | 1999-10-13 | Basf Aktiengesellschaft | Process for the preparation of sugar alcohols |
US20040002597A1 (en) * | 1999-03-16 | 2004-01-01 | Sudzucker Aktiengesellschaft | Catalytic process for the modification of carbohydrates, alcohols, aldehydes or polyhydroxy compounds |
US6808652B2 (en) | 2001-05-18 | 2004-10-26 | Korea Research Institute Of Chemical Technology | Modified ⊖-alumina-supported nickel reforming catalyst and its use for producing synthesis gas from natural gas |
US6693060B2 (en) * | 2001-05-18 | 2004-02-17 | Korea Research Institute Of Chemical Technology | Modified θ-Al2O3-supported nickel reforming catalyst and its use for producing synthesis gas from natural gas |
US20040142817A1 (en) * | 2001-05-18 | 2004-07-22 | Korea Research Institute Of Chemical Technology | Modified theta-alumina-supported nickel reforming catalyst and its use for producing synthesis gas from natural gas |
US20040171889A1 (en) * | 2001-06-11 | 2004-09-02 | Dominic Vanoppen | Method for the production of sorbit |
US20040176619A1 (en) * | 2001-06-11 | 2004-09-09 | Dominic Vanoppen | Ruthenium catalysts on a s102-based carrier material for catalytic hydrogenation of saccharides |
US7618917B2 (en) | 2001-06-11 | 2009-11-17 | Basf Aktiengesellschaft | Ruthenium catalysts |
US20080210222A1 (en) * | 2001-06-11 | 2008-09-04 | Basf Aktiengesellschaft | Ruthenium catalysts |
US7022824B2 (en) | 2001-06-11 | 2006-04-04 | Basf Aktiengesellschaft | Method for the production of sorbit |
EP2030680A1 (en) | 2001-06-11 | 2009-03-04 | Basf Se | Ruthenium catalysts on a SiO2 carrier for the catalytic hydrogenation of saccharides |
US20060009661A1 (en) * | 2002-12-11 | 2006-01-12 | Basf Aktiengesellschaft | Continuous method for the production of sugar alcohols |
US7163963B2 (en) | 2003-09-08 | 2007-01-16 | Conocophillips Company | Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts |
US20050054738A1 (en) * | 2003-09-08 | 2005-03-10 | Conocophillips Company | Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts |
US20080051573A1 (en) * | 2004-12-07 | 2008-02-28 | Thomas Hirth | Process for the Production of Sugar Alcohols |
WO2006061196A1 (en) * | 2004-12-07 | 2006-06-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Method for the production of sugar alcohols |
US7968704B2 (en) | 2004-12-07 | 2011-06-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of sugar alcohols |
US20080139383A1 (en) * | 2006-03-27 | 2008-06-12 | Catalytic Distillation Technologies | Hydrogenation of aromatic compounds |
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